Plastic composition.



- 1 STATES PATENT OFFICE.

JoNAs w. annswonrn, or EAST ORANGE; NEW JERSEY, ASSIGNOR rro coNnE'NsITE COMPANY OF AMERICA, or GLEN RIDGE, NEW JERSEY, A conrona-rronor NEW J RSEY.

iLAs'rIc oomrosrrroN.

Specification of Letters Patent.

REISSUED Patented Feb. 17, 1914.

No Drawing. Original application filed m 14,1909, Serial No. 496,060. Divided and apptication filed June a, 1911, Serial No. 630,894. Divided and this application filed May 2, 1912. Serial No. 694,644.

ToaZl echo-m, it may concern Be itknown that I, J ONAS. W. Answon'rn,

a citizen of the United States, and a resident of East Orange, in the county of Essex,

State of- New Jersey,"have invented certain new and useful Improvements in Plastlc Co'mposit'ions, 'of which the following is a description. V This application is a dIVlSlOnOf my application, Serial No. 630,894, filed June 2, 1911,

entitled Phenolic condensation products and: method offorming same,'wh1ch itself is a division of my application Serial-No. 496,060,

(filed May 14, 1909, entitled Composition and process of manufacturing the same. The original application Serial- No. 496,060 relates toand describes compositions for molding various articles, such as may be made from celluloid, hard rubber, and klndred substances, and also the production of synthetic resins. The latter is a hard fusible phenol resin madefrom phenol or cresol, by condensation with formaldehyde, and the former is an ultimate infusible condensation product of a phenol and formaldehyde or equivalents, preferably made from the phenol resin referred to, by reaction thereof with formaldehyde, preferably in polymerized form, in definite predetermlned percentages. The ultimate, infusible product referred to, is veryhard and chemically inert. It may have what I term a solid solvent element or plasticity ingredient incorporated. therewith, and my divisional application No. 630,894, referred to, describes and broadly claims compositions containing such an. element, and processes for makingthe same.

The present application relates to and will claim such compositions containing naphthale'ne or various chlorin substitution products of naphthalene, as the solid solvent or plasticity ingredient. Such products, while infusible, are sufiiciently plastic, on applica tion ofheat as hereinafterdescribed, to be shaped or pressed into form at suitable temperatures. This infusible, thermo-plastic product, as I term it, is preferably formed from-the phenol 'resin'referred to, but a product having many of theadvantages of this preferred product may be formed when various of the shellac substitutes or phenol'resins now known are used in the place of the particular ph enol resin referred to.

The degree of plasticity 'of the composition, upon subsequent application of heat, will vary 1n accordance with the plasticity ingredient' used, and the proportion of the same in the composition.

The fusible phenol resin, preferably used,

and processes for making the same, are fully dehydration before being used as an ingredient in the making of the ultimate infusible product, which dehydration requires about 400 F. of heat at atmospheric pressure. After such dehydration and removal of excess phenol it is a hard resin, very similar in texture to copal andkauri gum. It -is soluble in alLproportions in acetone, amyl, ethyl, methyl and butyl alcohol, amyl, ethyl and methyl acetate, acetic acid, acetylene tetrachlorid, and mono-nitro-benzene, (oil or mirbane), from which it remains' unchanged after evaporation of the solvents.

It is fusible and practically unchanged when heated to 420 F. It melts about 220 F, but has no sharp melting point passing through-various degrees of viscosity, until at 250 F. it may readily be poured and at 350 F .it becomes quite thinly fluid. It acts combines. It will; not form an' infusible condensation product when heated alone or with condensing agents, at any temperature. When mixed with formaldehyde, paraforma'ldehyde or trioxmethylene, and heated, it combinestherewith and forms a hard infusible mass, which, if not admixed'with other bodies, remains transparent and chemically inert. It will not, however, form such hard infusible mass when mixed with aldehydes in general, other than those mentioned, and if the percentage 'of formaldehyde or its polymers exceed about 7 g per cent., when the free phenol is less than 10 per cent., when no counteractin pressure is used, the excess escapes as bubb es in .the mass and renders the latter useless for some purposes.

'As described in my applications-referred as a weak acid toward bases with which it to, the ultimate infusible product is prefer ably formed by incorporating with such aphenol per cent. of the weight of the resin of polymerized, anhydrous formaldehyde, as trioxymethylene, or dioxymethylene, which is caused to dissolve therein. The phenol resin ferred to is also incorporatedwith the mass.

Substances which I have discovered to be efficacious for this purpose are naphthalene and some of its chloro derivatives, such as tetra-chloro-naphthalene. The final product solvent element contributes greater toughness to the product by counteracting the brittle nature of the ultimate product and renders the final mass plastic when heated, thus relieving internal stresses during the baking and hardening operations and subsequent cooling. By final product solvents, I include only substances which will dissolve the ultimate condensation product or combine therewith at the baking temperature, render it plastic at such temperature, and remain as a part of the product in the condition of solid solution or combination. Also, if desired, a water-combining element may be incorporated with the mass. This element takes care of traces of water which may be expelled during the baking operation. This results in a clearer and more transparent product, although I do not regard the inclusion of this element as absolutely essential. Examples of this class are benzoic anhydrid, phthalic anhydrid, and any such organic anhydrids as are soluble in and miscible with the mass, and are not decomposed at temperatures used. Having obtained the above mixture the same may be cast in suitable molds for the formation of the desired articles or for the formation of rods, sheets, tubes, or slabs, or the like, from which the desired articles may subsequently be made by heat and pressure, or by forming by tools. The molds and their contents are heated sufficiently to transform the product into a hard, infusible, chemically inert sub stance, the temperature to which the same is heated in practice varyin 400 Fahrenheit, depending on the treatment of the phenol resin before mixing the character of the water-combining element and the product solvent and the character of the molded article. The heating may be accomplished by casting in suitable steamjacketed molds, or by placing the molds and contents in suitable ovens for a time sulficient to allow the mixture to interact and harden. This time may vary within wide limits, depending on the thickness of the article and the character of the mass- Thin sheets and small articles may be hardened in resin .as described, from 5% to 10 melt at any temperature phenol resin used. Formaldehyde, polymer-' tions referred to, has various advantages between 260 and I tougher and less brittle in texture.

a few minutes, while larger masses and objects of special character may require gradual heating to the lowest temperature necessary for the reaction to take place andcontinued heating at such temperature, or at an elevated temperature, for several hours; The ultimate product so formed will not below that of its decomposition, but will soften and become sufficiently plastic at from 240 to 300 F., to be further shaped 'bypressing in suitable dies or molds. The degree of plasticity may be controlled to a certain extent by the nature of the solvent ingredient andproportions thereof, and by varying the proportions of the polymerized formaldehyde, added to the phenol resin. v

In the mixture of ingredients the polymerized formaldehyde is used in an amount which is sufficient to combine with nearly all the resin, so that there may be no excess of formaldehyde or polymer thereof to cause bubbling of the mass during the hardening operation. Such an amount may vary between 5 and 7%; per cent; of the weight of ized, may be used in place of the polymerized substance, in which case the polymerized formaldehydefis formed by evaporation during the process. It is usually impractical to make the phenol resin, entirely free from uncombined phenol, and the small variable percentage of phenol makes it necessary in the formation of the mixture for the ultimate product to vary the percentage of dioxy-- methylene, trioxymethylene, or paraformaldehyde in the'mixture with the resin, in accordance with the percentage of freephenol, ascertained by test- The phenol combines with a much greater proportion of polymerized formaldehyde than-does the phenol A resin. By varying the percentage ofthe polymerized formaldehyde as indicated; the free phenol inthe-phenol res n may allbe taken into combination. The product thus obtained after heating the phenol rcsin'and the other elements mentioned in proper proportions to a temperature of from 280 to 400 F. or higher, as statedvin my applicaover similar products, notably in that it softens sufiiciently to allow further shapmg,

as stated, at a temperature bet-ween 240 l*. and 300 F, while at the same time it is mfusible at any temperature lower than that of its decomposition, and also in that it 18 These results are largely attributable to the presence of the solid solvent or plasticity agent described. The product also has other advantages, as described in the applications referred to, in that it can be made of exact and definite ultimate composition, under perfect control,by the process particularly described,

without the necess ty of counteracting pressure, and the product so formed unusually free from gas bubbles.

The mass of the ultimate condensation product is normally of amber color and.

tion of suitable pigments. Chemically inert cheaper substances in powdered or fibrous form may be incorporated with the mass before baking in widely varying per cents.

when desired.

Preferred formulae for masses which are to be hardened in molds without subsequent pressing operations are as follows For light colored and transparent products.

Phenol resin 100 parts by weight. Naphthalene '5 ,to 10 i Polymerized formaldehyde 5 to 7 f Phenol resin. 100 Benzoic anhydrid 2 to ,4 Naphthalene 5 to 10 Tri-oxymethylene 5 to 8 j f For non-melting plastic compositions.

Phenol resin 100 partsby weight. Naphthalene 10 to 40 Paraformaldehyde.... .;;1a 5 to 10 Phenol resin 100 Naphthalene 10 to 20 Benzoic anhydrid 1 to 5 Paraformaldehyde 5 to 10 Phenol resin I 100 Tetra-chloro-naphthalene 10 to 25 Benzoic anhydrid 1 to 5 Paraformaldehyde 5 to 8 The specific'gravit'y of a similar composition, given as example, was found to be as follows j p Phenol resin 100 parts by weight Specific g r 8. vi t y,

Tetra-chloro-naphtha- 1.824. lene Opaleacent amber Paraformaldehyde 8 p color.

The specific gravity of the phenol resin used was found to be 1.240. This substance is transparent andvaries in tint from colorlessto a dark coffee shade,

In all of the formulae given above for the ultimate condensation product, the ingre v dients are mixed and freed from air bubbles by standing in molten condition or by vacuum treatment or by centrifugal treatment 'at temper'atures below'250 F. or freed .is heated for a short time to'a temperature of 300- to 350 F. The ingredients may also be heated to from 320 to-3509 F. u'nder counteracting pressure, as is done in the-art of vulcanizing rubber. When no counteracting pressure is used, from one-halfv to four hours isrequired before the final tem;

ture of the glycerin. zThe 'dients referred to also al perature may be, reached, this time varying with the thickness of the object molded.

Naphthalene, when in solid solution with the ultimate condensation product, does not volatilize perceptibly'at ordinary tempera tures, when within the proportions given in .the examples, although naphthalene does,

tend to volatilize slowly when alone. The" chloro-naphthalenes referred .to, when in solid solution with-the'ultirnate condensation product, do not volatilize either at room temperatures or at 219,? F. Naphthalene and the chloro derivatives arealso practically insoluble in water at room temperatures. .The practical non-water solubility of the solvent or plasticity ingredients referred to is. a valuable feature, because such ingredients cannot be removed from the mass to any appreciable extent, by water, even when the mass is in comminuted form, and furthermore masses made including such ingredients are not so susceptible to the influence of moisture in the atmosphere as are compositions containing ingredients such: as glycerin, which are soluble to a very great extent in water. Condensation products, containing glycerin,'for example, constantly attract'moisture from the atmosphere, because of the hygroscopic naplasticity ingrehave melting points substantially lower than .their boiling points which is an important property,

since thereby all the ingredients of the composition can be'mixed in fluidcondition, and the plasticity ingredient used will not volatilize away during the mixing or hardening reaction.

The term fusible appearing in the claims as qualifying a product such as my phenol resin, denotes a product which melts tion, as qualifying my ultimate product, denotes a substance WlllCh does not flow or become liquid, when heated to-any temperature, under atmospheric pressure. =VVhe1i an ultimate product solvent element is added, or an excess of phenol resin'is used as .a

v solvent for the ultimateproduct, as stated,

the mass'becomes sufficiently plastic to be readily pressed or molded to shape, but does not fuse.

-This application covers, as stated, compos tions containing naphthalene or various derivativesthereof as the solid solvent or plast city ingredient. The chloro derivatives are specifically claimed herein, and generic claims are also made, designed to cover naphthalene itself and such derivatives, which are capable-of performin the. desired solid solvent and plasticity unc tion in the coin osition, the nitro derivatives of napht alenef being specifically and becomes liquid, when sufliciently'lleat-g I ved,.under atmospheric pressure. The term 'infus'ible. in the claims of this 'applicaa Correction in Letters Patent No. 1,087,422.

claimed in my application Serial No. 630,894, referred to. As a suitable basis for such generic claims, it will be noted that naphthalene and its derivatives of the class referred to are condensed ring compounds having two closed chains with carbon atoms common to both, which limitation is peculiarly. descriptive of the substances referred to. "The word phenol as employed in the claims is intended to include the equivalents of phenol for the purposes of this invention, and the word formaldehyde is intended to include the polymers and other recognized equivalentsof formaldehyde.

Having now described my invention what I claim as new and desire. to protect by Letters Patent is 1. As a new composition of matter, a solid solution of 'an ultimate infusible Patent Olfice.

[SEAL] phenolic condensation product and a solid solvent therefor consisting of a condensed ring compound having two closed chains with carbon atoms common to both.

2. As a new composition of matter, a solid solution of an ultimate infusible phenolic condensation product and tetra- It is hereby certified that in Letters Patent No. 1,087,422., granted February 17, 1914, upon the application of Jonas W. Aylsworth, oi East Orange, New Jersey, for an improvement in Plastic Compositibns, an error appears in the printed specification reqifiring correction as follows: Page 2, line 91, after the word Formaldehyde insert the word not, and that the said Letters Patent should be read with this correction therein that the same may conform to the record'of the casein the J. r. NEWTON,

Acting Commissioner of Patenta. 

